WO2015176545A1 - Polyimide thermoplastique à mémoire de forme résistant à des températures élevées et son procédé de préparation - Google Patents

Polyimide thermoplastique à mémoire de forme résistant à des températures élevées et son procédé de préparation Download PDF

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WO2015176545A1
WO2015176545A1 PCT/CN2015/070308 CN2015070308W WO2015176545A1 WO 2015176545 A1 WO2015176545 A1 WO 2015176545A1 CN 2015070308 W CN2015070308 W CN 2015070308W WO 2015176545 A1 WO2015176545 A1 WO 2015176545A1
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temperature
shape memory
high temperature
resistant thermoplastic
raised
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PCT/CN2015/070308
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English (en)
Chinese (zh)
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冷劲松
肖鑫礼
刘彦菊
孔德艳
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哈尔滨工业大学
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the invention relates to a shape memory polyimide and a preparation method thereof.
  • a shape memory polymer is a polymer material that has an initial shape and is deformed and fixed under certain conditions, and is capable of sensing and responding to external changes of the stimulus to restore its original state.
  • various SMP materials such as shape memory polyurethane, shape memory polystyrene and shape memory epoxy resin have been developed in the world [Nature, 2010, 464, 267-270.], which are used in many fields such as smart textile, biomedical, aerospace and many other fields. More and more important.
  • Thermoplastic SMP has the advantages of easy processing and convenient use, and has excellent application and research prospects.
  • Shape memory fibers are prepared by using shape memory polyurethane such as Hu, and the clothes woven with these fibers have a unique shape memory effect and waterproof moisture permeability [Polymer, 2009, 50, 4424-4428.].
  • T g glass transition temperature
  • Polyimide (PI) is an aromatic heterocyclic polymer containing an imide characteristic group in the main chain structural unit, and has the advantages of high temperature resistance, radiation resistance, excellent mechanical properties, and diverse processing paths, and has been widely used. Automotive, microelectronics, aerospace and other fields [polyimide: relationship between chemistry, structure and properties and materials, Science Press, 2012.09.]. Therefore, shape memory thermoplastic polyimide has broad application prospects in many fields.
  • Thermoplastic polyimide generally refers to a soluble polyimide having a linear macromolecular structure with meltable and dissolvable processability.
  • General Electric Company of the United States introduced the thermoplastic polyetherimide Ultem, which has excellent soluble melt processing properties and still has strong market competitiveness.
  • thermoplastic polyetherimide Aurum with excellent heat resistance and melt processability.
  • the product was prepared by extrusion method and sold under the trade name Regulus.
  • the Changchun Yinghua Institute of the Chinese Academy of Sciences began researching polyimides in the 1960s and developed the YHPI series of thermoplastic polyimides. These polyimides have high toughness and horniness and can be molded and injection molded. They have been widely used in electrical insulation and wear resistant materials.
  • the Shanghai Synthetic Resin Research Institute has developed the Ratem series of polyimide engineering plastics since the 1970s, which can be used as bars, plates, tubes and processed or sintered parts.
  • Vaia et al. reported a thermosetting polyimide SMP with a T g around 220 ° C [Polymer 2013, 54, 391-402.]. However, there are no reports of SMP with T g >300 °C at home and abroad.
  • the object of the present invention is to solve the problem that the existing shape memory polymer has a low glass transition temperature T g , poor thermal properties and thermodynamic properties at high temperatures, and cannot be applied in a high temperature field, and provides a high temperature resistant thermoplastic shape memory polyacyl group. Imine and its preparation method.
  • thermoplastic shape memory polyimide prepared by using 4,4'-(hexafluoroisopropene) diphthalic anhydride and 4,4'-diaminodiphenyl ether as a reactive monomer; The amount ratio of the 4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer was 1:1.
  • thermoplastic shape memory polyimide The structural formula of a high temperature resistant thermoplastic shape memory polyimide is:
  • n is from 128 to 172.
  • a method for preparing a high temperature resistant thermoplastic shape memory polyimide is accomplished by the following steps:
  • the volume ratio of the amount of the 4,4'-diaminodiphenyl ether monomer to the N,N'-dimethylacetamide in the first step is (0.1 mmol to 0.2 mmol): 1 mL;
  • sol-gel polyamic acid 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 3 to 6 times at room temperature and stirring speed was 300 r/min. Stirring for 25 to 30 hours under conditions of ⁇ 400/min to obtain a sol-gel polyamic acid;
  • the ratio of the amount of the 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer in the diamine solution is 1:1;
  • the sol-gel-like polystyrene acid is poured onto the substrate, and the temperature is raised from room temperature to 60 ° C to 90 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and The temperature is maintained at 60 ° C ⁇ 90 ° C for 1 h ⁇ 2 h; then at 1 ° C / min ⁇ 2 ° C / min heating rate to 120 ° C ⁇ 140 ° C, and at a temperature of 120 ° C ⁇ 140 ° C for 1 h ⁇ 2h Then, the temperature is raised to 170 ° C ⁇ 190 ° C at a heating rate of 1 ° C / min ⁇ 2 ° C / min, and the temperature is maintained at 170 ° C ⁇ 190 ° C for 1 h ⁇ 2 h; and then 1 ° C / min ⁇ 2 ° C / min The heating rate is up to 220 ° C ⁇ 250 ° C,
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally at a temperature of 120 ° C to 180 ° C. The lower temperature is heated for 360 min to 600 min to obtain a high temperature resistant thermoplastic shape memory polyimide.
  • the chemical reaction formula in the second step of the present invention is:
  • the chemical reaction formula in the fourth step of the present invention is:
  • the high temperature thermoplastic shape memory polyimide prepared by the invention has a glass transition temperature T g of 313 ° C to 319 ° C, which makes it applicable to the field of high temperature shape memory polymers;
  • the material prepared by the invention can be dissolved in an organic solvent such as chloroform, toluene, xylene or N,N'-dimethylacetamide at room temperature at 25 ° C, and has excellent processability for low-temperature solvent processing;
  • the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared by the invention is 5% when the mass loss is 5%, which indicates that the material has thermal stability at high temperature and can be used for a long time in a high temperature environment;
  • the high temperature resistant thermoplastic shape memory polyimide prepared by the invention has excellent thermodynamic effect, the storage modulus is greater than 2 GPa at a normal temperature of 30 ° C glass state, and the storage modulus at a high temperature (T g + 20 ° C) rubber state. More than 6 MPa; the stability of the size and shape of the structural member at high temperature is ensured;
  • the high temperature resistant thermoplastic shape memory polyimide prepared by the invention has excellent high and low temperature resistance, and its shape memory performance is not lowered after being heated for 100 hours in an alternating atmosphere of -120 ° C to 120 ° C.
  • the present invention provides a high temperature resistant thermoplastic shape memory polyimide.
  • Example 1 is an infrared spectrum diagram of a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
  • Example 2 is a loss factor diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
  • Example 3 is a storage modulus diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
  • Example 4 is a thermogravimetric analysis diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1;
  • Example 5 is a temporary shape obtained by bending a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 at 310 ° C and fixing at room temperature;
  • Example 6 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 2 s on a hot stage at 310 ° C;
  • Example 7 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 10 s on a hot stage at 310 ° C;
  • Example 8 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 13 s on a hot stage at 310 ° C;
  • Example 9 is a shape recovery state of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 16 s on a hot stage at 310 ° C;
  • Figure 10 is a view showing the shape of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 restored to its original shape after 23 seconds on a hot stage at 310 °C.
  • the present embodiment is a high temperature resistant thermoplastic shape memory polyimide comprising 4,4'-(hexafluoroisopropene) dinonanhydride and 4,4'-diaminodiphenyl ether as a reactive monomer Prepared; the amount ratio of the 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer is 1:1.
  • thermoplastic shape memory polyimide This embodiment differs from the specific embodiment in that the structural formula of a high temperature resistant thermoplastic shape memory polyimide is:
  • n is from 128 to 172.
  • the other steps are the same as in the first embodiment.
  • This embodiment differs from the second embodiment in that a high temperature resistant thermoplastic shape memory polyimide has a weight average molecular weight of 77.8 kg/mol to 104.6 kg/mol.
  • the other steps are the same as in the second embodiment.
  • This embodiment is a method for preparing a high temperature resistant thermoplastic shape memory polyimide, which is completed as follows:
  • the volume ratio of the amount of the 4,4'-diaminodiphenyl ether monomer to the N,N'-dimethylacetamide in the first step is (0.1 mmol to 0.2 mmol): 1 mL;
  • sol-gel polyamic acid 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 3 to 6 times at room temperature and stirring speed was 300 r/min. Stirring for 25 to 30 hours under conditions of ⁇ 400/min to obtain a sol-gel polyamic acid;
  • the ratio of the amount of the 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer to the 4,4'-diaminodiphenyl ether monomer in the diamine solution is 1:1;
  • the sol-gel-like polystyrene acid is poured onto the substrate, and the temperature is raised from room temperature to 60 ° C to 90 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and The temperature is maintained at 60 ° C ⁇ 90 ° C for 1 h ⁇ 2 h; then at 1 ° C / min ⁇ 2 ° C / min heating rate to 120 ° C ⁇ 140 ° C, and at a temperature of 120 ° C ⁇ 140 ° C for 1 h ⁇ 2h Then, the temperature is raised to 170 ° C ⁇ 190 ° C at a heating rate of 1 ° C / min ⁇ 2 ° C / min, and the temperature is maintained at 170 ° C ⁇ 190 ° C for 1 h ⁇ 2 h; and then 1 ° C / min ⁇ 2 ° C / min The heating rate is up to 220 ° C ⁇ 250 ° C,
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally at a temperature of 120 ° C to 180 ° C. The lower temperature is heated for 360 min to 600 min to obtain a high temperature resistant thermoplastic shape memory polyimide.
  • the high temperature thermoplastic shape memory polyimide prepared by the embodiment has a glass transition temperature T g of 313 ° C to 319 ° C, which can be applied to the field of high temperature shape memory polymers;
  • the material prepared in the present embodiment can be dissolved in an organic solvent such as chloroform, toluene, xylene or N,N'-dimethylacetamide at room temperature at 25 ° C, and has excellent processability for low-temperature solvent processing. ;
  • the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared by the embodiment is 5% when the mass loss is 5%, which indicates that the material has thermal stability at high temperature and can be used for a long time in a high temperature environment;
  • the high temperature resistant thermoplastic shape memory polyimide prepared by the embodiment has excellent thermodynamic effect, the storage modulus is greater than 2 GPa at a normal temperature of 30 ° C glass state; the storage modulus at a high temperature of 337 ° C rubber state is greater than 6 MPa; The stability of the size and shape of the structural member at high temperatures;
  • the high temperature resistant thermoplastic shape memory polyimide prepared by the present embodiment has excellent high and low temperature resistance, and its shape memory performance is not lowered after being heated for 100 hours in an alternating atmosphere of -120 ° C to 120 ° C.
  • This embodiment provides a high temperature resistant thermoplastic shape memory polyimide.
  • Embodiment 7 This embodiment differs from one of the fifth or sixth embodiment in that: in step 3, the sol-gel polyamic acid is dried in a vacuum drying oven at 55 ° C to 75 ° C for 1.5 h to 2 h. A sol-gel-like polyamic acid containing no bubbles was obtained. The other steps are the same as the fifth or sixth embodiment.
  • BEST MODE 8 This embodiment differs from one of the fifth to seventh embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the sol-gel-like bubble-free is used.
  • the polyamic acid is poured onto the substrate, and the temperature is raised from room temperature to 70 ° C to 80 ° C at a heating rate of 1 ° C / min to 2 ° C / min, and the temperature is maintained at 70 ° C to 80 ° C for 1 h to 2 h;
  • the heating rate of °C/min ⁇ 2°C/min is raised to 130°C ⁇ 140°C, and the temperature is maintained at 130°C ⁇ 140°C for 1h ⁇ 2h; then the temperature is raised at the heating rate of 1°C/min ⁇ 2°C/min.
  • This embodiment differs from one of the fifth to eighth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min.
  • the temperature was raised to 60 ° C at room temperature, and the temperature was maintained at 60 ° C for 2 h; then the temperature was raised to 120 ° C at a heating rate of 1 ° C / min, and kept at a temperature of 120 ° C for 1 h; then at a heating rate of 1 ° C / min
  • the temperature is raised to 170 ° C, and the temperature is maintained at 170 ° C for 1 h; then at a temperature increase rate of 1 ° C / min to 220 ° C, and the temperature is maintained at 220 ° C for 1 h; and then heated at a temperature increase rate of 1 ° C / min to 270 °C, and kept at a temperature of 270 ° C for 1 h; then at a temperature increase rate of 1 ° C / min to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at a temperature of 1 ° C / min from the temperature of 330 ° C
  • the substrate
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min. The temperature was raised to 60 ° C at room temperature, and the temperature was kept at 60 ° C for 2 h; then the temperature was raised to 120 ° C at a heating rate of 1 ° C / min, and the temperature was 120 ° C.
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min.
  • the temperature was raised from room temperature to 70 ° C, and the temperature was kept at 70 ° C for 2 h; then the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then at a heating rate of 1 ° C / min
  • the temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 1 h; then at a temperature increase rate of 2 ° C / min to 250 ° C, and the temperature is maintained at 250 ° C for 1 h; and then heated at a rate of 2 ° C / min to 290 °C, and kept at a temperature of 290 ° C for 1 h; then at a temperature increase rate of 2 ° C / min to 320 ° C, and at a temperature of 320 ° C for 1 h; finally at a temperature of 2 ° C / min from 320 ° C
  • the substrate was cooled to room temperature to obtain a
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min.
  • the temperature is raised from room temperature to 80 ° C, and the temperature is kept at 80 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min
  • the temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 230 ° C, and the temperature is maintained at 230 ° C for 1 h; and then heated at a temperature increase rate of 2 ° C / min to 280 ° C, and incubated at 280 ° C for 1 h; then at 2 ° C / min heating rate to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at 2 ° C / min cooling rate from a temperature of 330
  • the temperature was lowered to room temperature at ° C to obtain a
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min.
  • the temperature is raised from room temperature to 80 ° C, and the temperature is kept at 80 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min
  • the temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 230 ° C, and the temperature is maintained at 230 ° C for 2 h; and then heated at a temperature increase rate of 2 ° C / min to 280 ° C, and incubated at 280 ° C for 1 h; then at 2 ° C / min heating rate to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at 2 ° C / min cooling rate from a temperature of 330
  • the temperature was lowered to room temperature at ° C to obtain a
  • This embodiment differs from one of the fifth to thirteenth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min.
  • the temperature is raised from room temperature to 80 ° C, and the temperature is kept at 80 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min
  • the temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 1 ° C / min to 240 ° C, and the temperature is maintained at 240 ° C for 1 h; and then heated at a temperature increase rate of 1 ° C / min to 280 ° C, and incubated at a temperature of 280 ° C for 1 h; then at a temperature increase rate of 1 ° C / min to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at a rate of 1 ° C / min from the temperature of 330
  • the temperature was lowered to room
  • This embodiment differs from one of the fifth to fourteenth embodiments in that: in step 4, a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min.
  • the rate starts to increase from room temperature to 70 ° C, and the temperature is maintained at 70 ° C for 2h; then at a temperature increase rate of 1 ° C / min to 130 ° C, and the temperature is maintained at 130 ° C for 2h; and then heated at a temperature of 1 ° C / min to 180 ° C, And the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 240 ° C, and the temperature is maintained at 240 ° C for 1 h; then at a temperature increase rate of 2 ° C / min to 280 ° C, and at the temperature The temperature was kept at 280 ° C for 1 h; the temperature was raised to 330 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 330 ° C for 1 h; finally, the temperature was lowered from 330 ° C to room temperature at a cooling rate of 2 ° C / min.
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 1 ° C/min.
  • the temperature is raised from room temperature to 70 ° C, and the temperature is kept at 70 ° C for 2 h; then the temperature is raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 130 ° C for 2 h; then the temperature is raised at 1 ° C / min
  • the temperature is raised to 180 ° C, and the temperature is maintained at 180 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 240 ° C, and the temperature is maintained at 240 ° C for 1 h; and then heated at a temperature increase rate of 2 ° C / min to 280 ° C, and incubated at 280 ° C for 1 h; then at 2 ° C / min heating rate to 330 ° C, and at a temperature of 330 ° C for 1 h; finally at 2 ° C / min cooling rate from a temperature of 330
  • the temperature was lowered to room temperature at ° C to obtain a
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate at a heating rate of 1 ° C/min.
  • the temperature was raised from room temperature to 80 ° C, and the temperature was kept at 80 ° C for 2 h; then the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and kept at a temperature of 140 ° C for 2 h; and then at a heating rate of 1 ° C / min
  • the temperature is raised to 190 ° C, and the temperature is maintained at 190 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 250 ° C, and the temperature is maintained at 250 ° C for 1 h; and then heated at a temperature increase rate of 2 ° C / min to 290 °C, and kept at a temperature of 290 ° C for 2h; then heated to 340 ° C at a temperature increase rate of 2 ° C / min, and incubated at a temperature of 340 ° C for 2 h; finally at a temperature drop of 2 ° C / min from a temperature of 340 ° C
  • step 4 a sol-gel-like polystyrene-free polyamic acid is poured onto a substrate, and the temperature is raised at 2 ° C/min.
  • the temperature is raised from room temperature to 90 ° C, and the temperature is maintained at 90 ° C for 2 h; then the temperature is raised to 140 ° C at a temperature increase rate of 2 ° C / min, and the temperature is maintained at 140 ° C for 2 h; then the temperature is raised at 2 ° C / min
  • the temperature is raised to 190 ° C, and the temperature is maintained at 190 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 250 ° C, and the temperature is maintained at 250 ° C for 2 h; and then heated at a temperature increase rate of 2 ° C / min to 290 ° C, and incubated at a temperature of 290 ° C for 2 h; then at a temperature increase rate of 2 ° C / min to 340 ° C, and at a temperature of 340 ° C for 2 h; finally at a rate of 2 ° C / min from the temperature of 340
  • the temperature was lowered to
  • This embodiment differs from one of the fifth to nineteenth embodiments in the specific embodiment in that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N'- The volume ratio of the dimethylacetamide solvent was 0.1 mmol: 1 mL.
  • the other steps are the same as the specific embodiments 5 to 19.
  • This embodiment differs from the specific embodiment 6 to 21 in that the amount of the 4,4'-diaminodiphenyl ether monomer in step 1 is N, N' The volume ratio of the dimethylacetamide solvent was 0.14 mmol: 1 mL.
  • the other steps are the same as the specific embodiments 6 to 20.
  • This embodiment differs from one of the fifth to twenty-first embodiments in the following manner: the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N. The volume ratio of '-dimethylacetamide solvent was 0.15 mmol: 1 mL. The other steps are the same as the specific embodiments 5 to 21.
  • This embodiment differs from one of the fifth to twenty-fourth embodiments in the specific embodiment in that the amount of the substance of the 4,4'-diaminodiphenyl ether monomer described in the first step is N, N.
  • the volume ratio of the '-dimethylacetamide solvent was 0.18 mmol: 1 mL.
  • the other steps are the same as the specific embodiments 5 to 24.
  • This embodiment differs from one of the fifth to twenty-seventh embodiments in that: in step 5, the substrate of the polyamide film is placed in distilled water to make the polyamide film from the substrate of the polyamide film. After falling off, the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 130 ° C to 170 ° C for 450 min to 550 min to obtain a high temperature resistant thermoplastic shape memory polyimide. The other steps are the same as the specific embodiments 5 to 27.
  • Example 1 A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
  • sol-gel polyamic acid 1.9 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 400 r / Stirring under the condition of min for 28 h to obtain a sol-gel polyamic acid;
  • thermal imidization the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 80 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 80 ° C for 2 h; Then, the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then the temperature was raised to 190 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 190 ° C for 2 h; The heating rate of °C/min is up to 250 °C, and the temperature is maintained at 250 ° C for 1 h; then the temperature is raised to 290 ° C at a heating rate of 2 ° C / min, and the temperature is maintained at 290 ° C for 2 h; then 2 ° C / min The heating rate is raised to 340 ° C, and the temperature is kept at 340 ° C for 2
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 120 ° C for 500 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
  • the high temperature thermoplastic shape memory polyimide prepared in Example 1 was measured by gel permeation chromatography to have a weight average molecular weight of 101 kg/mol.
  • thermoplastic shape memory polyimide prepared in Example 1 was measured by gel permeation chromatography:
  • FIG. 1 is an infrared spectrum diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1.
  • symmetric stretching vibration peak (v s C O)
  • an absorption peak at 1382cm -1 (V CN) CN bond stretching vibration at 1110cm -1 imide ring was bending vibration absorption peaks (v CO).
  • FIG. 2 is a loss factor diagram of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1. . It can be seen from FIG. 2 that the glass transition temperature T g of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 is 317 ° C, and thus it can be seen that the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 can be applied. To the high temperature field.
  • FIG. 3 is a storage modulus diagram of the high temperature resistant thermoplastic shape memory polyimide; It can be seen that the modulus change curve shows two platforms in the high and low temperature sections, and the storage modulus at room temperature, that is, the glass state at 30 ° C is 2243 MPa; the storage modulus at the high temperature of 337 ° C, that is, the rubber state at T g + 20 ° C About 9.7 MPa; the storage modulus drops sharply between the two platforms, corresponding to the glass transition process of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1, the sharp change of the modulus is the polymer The necessary conditions for shape memory properties.
  • the corresponding storage modulus at 287 ° C, ie T g -30 ° C, is 1142 MPa, which ensures that the high temperature resistant thermoplastic shape memory polyimide of Example 1 is used as a structural material, which is higher than the current SMP materials.
  • the change in modulus within the use temperature range is relatively small, and the dimensional and shape stability of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 as a structural member is ensured.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was tested using a thermogravimetric analyzer as shown in FIG. 4; and FIG. 4 is a thermogravimetric analysis diagram of the high temperature resistant thermoplastic shape memory polyimide. 4, the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was 525 ° C when the mass loss was 5%, and the residual temperature at 800 ° C was 56.2%, indicating the high temperature resistance prepared in Example 1. Thermoplastic shape memory polyimides have excellent heat resistance.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 was tested using a high temperature hot stage, as shown in FIGS. 5 to 10;
  • FIG. 5 is a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 at 310.
  • the temporary shape prepared by bending at ° C and fixed at room temperature;
  • FIG. 6 is the shape recovery of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 2 s on a hot stage at 310 ° C;
  • FIG. 7 is the resistance of Example 1 The shape recovery of the high temperature thermoplastic shape memory polyimide after 10s on the hot stage at 310 ° C;
  • FIG. 5 is a high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 at 310.
  • the temporary shape prepared by bending at ° C and fixed at room temperature
  • FIG. 6 is the shape recovery of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 1 after 2 s on a hot stage at 310 ° C
  • FIG. 7 is the resistance of Example
  • Example 2 A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
  • sol-gel polyamic acid 1 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 4 portions at room temperature and the stirring speed was 300 r/min. Stirring under the conditions of 26 h to obtain a sol-gel polyamic acid;
  • thermal imidization the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 70 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 70 ° C for 2 h; Then, the temperature was raised to 140 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then the temperature was raised to 180 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 180 ° C for 1 h; The heating rate of °C/min is up to 250 °C, and the temperature is maintained at 250 ° C for 1 h; then the temperature is raised to 290 ° C at a heating rate of 2 ° C / min, and the temperature is maintained at 290 ° C for 1 h; then 2 ° C / min The heating rate was raised to 320 ° C, and the temperature was kept at 320 ° C for 1 h
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C for 400 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
  • the weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 was measured by gel permeation chromatography to be 77.8 kg/mol.
  • thermoplastic shape memory polyimide prepared in Example 2 was measured using a gel permeation chromatograph:
  • the glass transition temperature T g of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 was 313 °C.
  • the storage modulus at a normal temperature of 30 ° C in a glass state is 2012 MPa; the storage modulus at a high temperature of 333 ° C, that is, T g + 20 ° C in a rubber state is about 6.2 MPa.
  • the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 at a mass loss of 5% was 522 ° C, and the residue at 800 ° C was 53.5%.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 2 was folded 180° on a hot plate at 310 ° C to return to the original shape for 33 s.
  • Example 3 A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
  • sol-gel polyamic acid 1.5 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 350 r / Stirring under the condition of min for 26 h to obtain a sol-gel polyamic acid;
  • thermal imidization the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 80 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 80 ° C for 2 h; Then, the temperature was raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 130 ° C for 2 h; then the temperature was raised to 180 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 180 ° C for 2 h; The heating rate of °C/min is up to 230 °C, and the temperature is kept at 230 °C for 2 h; then the temperature is raised to 280 °C at a heating rate of 2 °C/min, and the temperature is maintained at 280 °C for 1 h; then at 2 °C/min.
  • the heating rate was raised to 330 ° C, and the temperature was maintained at 330 ° C for 1 h; finally, the temperature was lowered from 330 ° C to room temperature at a cooling rate of 2 ° C / min to obtain a substrate of a polyamide film.
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C for 360 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
  • the weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 was measured by gel permeation chromatography to be 88.8 kg/mol.
  • thermoplastic shape memory polyimide prepared in Example 3 was measured using a gel permeation chromatograph:
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 had a glass transition temperature Tg of 314 °C.
  • the storage modulus at room temperature, that is, the glass state at 30 ° C is 2126 MPa; the storage modulus at the high temperature of 334 ° C, that is, T g + 20 ° C in the rubber state is about 7.1 MPa.
  • the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 at a mass loss of 5% was 524 ° C, and the residue at 800 ° C was 54.5%.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 3 was folded 180° on a hot plate at 310 ° C to return to the original shape for 31 s.
  • Example 4 A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
  • sol-gel polyamic acid 1.7 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 300 r / Stirring under the condition of min for 26 h to obtain a sol-gel polyamic acid;
  • thermal imidization the sol-gel-like polystyrene acid is poured onto the substrate, the temperature is raised from room temperature to 70 ° C at a heating rate of 1 ° C / min, and the temperature is maintained at 70 ° C for 2 h; Then, the temperature was raised to 130 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 130 ° C for 2 h; then the temperature was raised to 180 ° C at a heating rate of 1 ° C / min, and the temperature was maintained at 180 ° C for 2 h; The heating rate of °C/min is up to 240 °C, and the temperature is kept at 240 °C for 1 h; then the temperature is raised to 280 °C at a heating rate of 2 °C/min, and the temperature is maintained at 280 °C for 1 h; then at 2 °C/min.
  • the heating rate was raised to 330 ° C, and the temperature was maintained at 330 ° C for 1 h; finally, the temperature was lowered from 330 ° C to room temperature at a cooling rate of 2 ° C / min to obtain a substrate of a polyamide film.
  • the substrate of the polyamide film is placed in distilled water, the polyamide film is peeled off from the substrate of the polyamide film, and the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C for 400 min. A high temperature resistant thermoplastic shape memory polyimide is obtained.
  • the weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 4 was measured by gel permeation chromatography to be 94.2 kg/mol.
  • thermoplastic shape memory polyimide prepared in Example 4 was measured using a gel permeation chromatograph:
  • High Temperature Thermoplastic shape memory Preparation Example 4 polyimide has a glass transition temperature T g of 315 °C.
  • the storage modulus at room temperature, that is, the glass state at 30 ° C is 2176 MPa; the storage modulus at the high temperature of 335 ° C, that is, T g + 20 ° C in the rubber state is about 7.8 MPa.
  • the decomposition temperature of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 4 at a mass loss of 5% was 523 ° C, and the residue at 800 ° C was 56.5%.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 4 was folded 180° on a hot plate at 310 ° C to return to the original shape for 38 s.
  • Example 5 A method for preparing a high temperature resistant thermoplastic shape memory polyimide was carried out by the following steps:
  • sol-gel polyamic acid 2.0 mmol of 4,4'-(hexafluoroisopropene) diphthalic anhydride monomer was added to the diamine solution in 5 portions at room temperature and the stirring speed was 400 r/ Stirring under the condition of min for 28 h to obtain a sol-gel polyamic acid;
  • the sol-gel-like polystyrene acid without bubbles is poured onto the substrate, and the temperature is raised from room temperature to 90 ° C at a heating rate of 2 ° C / min, and the temperature is maintained at 90 ° C for 2 h; Then, the temperature was raised to 140 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 140 ° C for 2 h; then the temperature was raised to 190 ° C at a heating rate of 2 ° C / min, and the temperature was maintained at 190 ° C for 2 h; The heating rate of °C/min is up to 250 °C, and the temperature is kept at 250 °C for 2 h; then the temperature is raised to 290 °C at a heating rate of 2 °C/min, and the temperature is maintained at 290 °C for 2 h; then at 2 °C/min.
  • the heating rate was raised to 340 ° C, and the temperature was maintained at 340 ° C for 2 h; finally, the temperature was lowered from 340 ° C to room temperature at a cooling rate of 2 ° C / min to obtain a substrate of a polyamide film.
  • the substrate of the polyamide film is placed in distilled water to remove the polyamic acid film from the substrate of the polyamide film, and then the polyamide film is rinsed off with distilled water, and finally heated at a temperature of 180 ° C. At 360 min, a high temperature resistant thermoplastic shape memory polyimide was obtained.
  • the weight average molecular weight of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 was measured by gel permeation chromatography to be 104.6 kg/mol.
  • thermoplastic shape memory polyimide prepared in Example 5 was measured using a gel permeation chromatograph:
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 had a glass transition temperature T g of 319 °C.
  • the storage modulus at room temperature, that is, the glass state at 30 ° C is 2568 MPa; the storage modulus at the high temperature of 339 ° C, that is, T g + 20 ° C in the rubber state is about 8.7 MPa.
  • the decomposition temperature at which the mass loss resistance of the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 was 5% was 526 ° C, and the residue at 800 ° C was 57.6%.
  • the high temperature resistant thermoplastic shape memory polyimide prepared in Example 5 was folded 180° on a hot plate at 310 ° C to return to the original shape for 35 s.

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Abstract

Cette invention concerne un polyimide thermoplastique à mémoire de forme résistant à des températures élevées et son procédé de préparation, et concerne plus spécifiquement un polyimide existant et son procédé de préparation. L'invention vise à résoudre le problème selon lequel un polymère à mémoire de forme existant est inapplicable dans un domaine à températures élevées en raison d'une basse température de transition vitreuse, Tg, et de médiocres propriétés thermiques et propriétés thermodynamiques à températures élevées. La solution selon l'invention porte sur un polyimide thermoplastique à mémoire de forme résistant à des températures élevées qui est préparé à l'aide d'un anhydride 4,4 '-(hexafluoroisopropylidène)diphtalique et d'un 4,4 '-diaminodiphényléther à titre de monomères réactifs et a la formule structurale représentée par la formule (I). Ce procédé de préparation comprend les étapes suivantes : 1. dissolution des monomères de 4,4'-diaminodiphényléther; 2. préparation d'un acide polyamique de type sol-gel; 3. élimination des bulles d'air résiduaires; 4. imidation thermique; et 5. démoulage. La présente invention produit un polyimide thermoplastique à mémoire de forme résistant à des températures élevées.
PCT/CN2015/070308 2014-05-23 2015-01-08 Polyimide thermoplastique à mémoire de forme résistant à des températures élevées et son procédé de préparation WO2015176545A1 (fr)

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CN103980492B (zh) * 2014-05-23 2016-06-29 哈尔滨工业大学 一种耐高温热塑性形状记忆聚酰亚胺的制备方法
CN105254888B (zh) * 2015-11-23 2019-01-22 厦门理工学院 聚酰亚胺离聚物及其制备方法
CN105542460B (zh) * 2016-03-01 2018-03-27 哈尔滨工业大学 一种高温聚酰亚胺热缩管及其制备方法
CN105778092B (zh) * 2016-03-09 2018-03-16 哈尔滨工业大学 一种聚醚酰亚胺高温热缩管及其制备方法
CN106902652B (zh) * 2017-03-21 2019-12-27 中国科学院兰州化学物理研究所 一种具有形状记忆性能的气体分离膜
CN110894294B (zh) * 2019-12-09 2021-01-08 中国科学院长春应用化学研究所 一种耐高温含氟聚酰亚胺热缩管及其制备方法
CN113417145B (zh) * 2021-05-17 2022-03-15 东华大学 一种双向形状记忆聚酰亚胺纤维布及其制备方法
CN114045028A (zh) * 2021-12-10 2022-02-15 东华大学 一种可变形热塑性复合材料及其制备方法
CN114773601B (zh) * 2022-05-24 2023-08-22 哈尔滨工业大学 高Tg、高模量形状记忆阻燃聚酰亚胺及其制备方法和应用

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